Dialkylaminoindanyl methylcarbamate



United StatesPatentOfiice 3,612,067

Patented Dec. 5, 1961 The following examples illustrate the present invention 3,012,067 but are not to be construed as limiting. DIALKYLAMINOINDANYL METHYL- CARBAMATE EXAMPLE 1 Warren W. Kaeding, Concord, Califi, assignor to The d h Dow Chemic a1 Company, Midland, Mich. a comoxw 7 zmethylammo-4 m anyl met ylcarbamate tion of Delaware oooNnorr, No Drawing. Filed- Dec. 21, 1959, Ser. No. 860,589 CH2 4 Claims. (Cl. 260-479) This invention is concerned with dialkylaminoindanyl 1 methylcarbamates having the structure OCONHCH; (OHmN 2 milliliters (0.035 mole) of methyl isocyanate and a few drops of triethylarnine catalyst were added at room temperature with stirring to a solution of 4.5 grams (0.025 mole) of 7-dimethylaminoindanol in 4050 milli- NR liters of methylene chloride. The reaction mixture was allowed to stand for 2 days at room temperature and In this and succeeding formula R represents a lowe althe solvent evaporated. therefrom to obtain a 7-dimethylkyl radical containing from 1 to 4 carbon atoms, incluamino-4-indaflyl metbylcafbamate PIQCIUct a5 a White sive. The products f th present invention are hi solid residue. The latter was recrystallized from hexane solids soluble inorganic solvents such as alcohols, acei0 Obtain Purified Product melting at 3 C- tone, chloroform and dimethylformamide and substan- Th6 Produbt bad elemental analyses in Pefbfiilt as tially insoluble in water. The compounds of the pres- IOWSI ent invention are useful for the control of plant and water-infesting pests. Carbon Hydro- Nitrogen The dialkylarninoindanyl methylcarbamates may be 7 7 gen prepared by reacting a dialkylaminoindanol having the Th 6",.64 7. 74 11.96 structure Fo ii d 63.59 7. 73 11.82

l 311, EXAMPLE 2 7-di-normal-butylamino-4-indanyl methylcarbamate oooNnong \CH2 CH2 NR: CH

2 with methyl isocyanate in the presence of a tertiary amine 40 catalyst. In carrying out the reaction, the appropriate CH2 dialkylaminoindanol is reacted with a substantially equi- (OH3CH2CH2OH2)2N molar proportion of methyl isocyanatein an inert solvent in a Similar manner, 35 {milliliters 061 mole) of and 111 Presence of a catalytlc amount 0f ternary methyl isocyana-te and a few drops of triethylamine cataamine. suitable solvents for carrying out b reaction lyst were added at room temperature with stirring to a include dunethylrormam1de, methylene chloride, hexane Solution of 109 grams 0042 mole) f 7 di- 1 b 1 and trifithylamine- Suitable Catalysts for carrying out amino-4-indanol in about milliliters of methylene the reaction include tlietbylamifie, trimetbyla-mine and chloride. The reaction mixture was allowed to stand at Py Tbe reaction y be carried out in the room temperature overnight and thereafter the solvent Pemblfe range 0f from about 10 at 391105" 50 removed by vaporization to obtain a 7-di-normal-butyl- Pbefic p 171E reaction is usually Complete in a amino-4-indanyl methylc'arbamate product as a white P of from about 50 minutes to 24 hours although solid residue. The latter was recrystallized from hexane the mixture may be allowed to stand for several days to obtain a purified product melting at 79-8l C. The

witbout dbtffmem- Alternatively, the reaction y be product had elemental analyses in percent as follows: earned out in the temperature range of from about 50 to 75 C. at pressures above atmospheric, such as that present in a closed vessel. Under these conditions, the reaction is usually complete in a period of from about Carbon Hydrogen N ltrogen 15 minutes to about 1 /2 hours. After completion of $23531:::::::::::::::::::::::::::::: 3123 3:22 3:?3 the reaction, the solvent is removed by vaporization to recover the desired dimethylaminoindanyl methylcar- EXAMPLE 3 3 gigi gf g iiggggggi g: may 0e purified 7-dz'isobutylamin0-4-indanyl methylcarbamate In a preferred method for carrying out the reaction, In a manner similar to that previously described, 4.5 about 10 percent molar excess of methyl isocyanate and milliliters (0.079 mole) of methyl isocyanate and a few a few drops of triethylamine catalyst are added at room drops of triethylamine catalyst were added to a solutemperature with stirring to a solution of 4-dimethyltion of 15 grams (0.057 mole) of 7-diisobutylamino-4- aminoindanol in an inert solvent. The reaction mixture indanol in 100 milliliters of pentane. The reaction mixis allowed to stand at room temperature overnight and ture Was allowed to stand overnight, thereafter decolorthe solvent removed by vaporization to recover the deized with activated charcoal and the solvent then evapsired product. The latter may be purified by recrystalorated from the decolorized solution to obtain the delization. sired 7-diisobutylamino-4-indanyl methylcarbamate prodnot as an amber colored oil. The oil was allowed to stand for about 2 weeks at room temperature whereupon it crystallized into a waxy tan colored solid which melted in the temperature range of from 68 to 75 C.

' EXAMPLE 4 In a manner similar to the foregoing, the following compounds are prepared:

7-diethylarnino-4-indanyl methylcarbamate by the reaction of 7-diethylamino-4-indanol and methyl isocyanate in the presence of triethylamine catalyst.

7-diisopropylamino-4-indanyl methylcarbamate by the reaction of 7-diisopropylamino-4-indanol and methyl iso cyanate in the presence of triethylamine catalyst.

7-di-normal-propylamino-4 indanyl methylcarbamate by the reaction of 7-di-normal-propylamino-4-indanol and methyl isocyanate in the presence of triethylamine catalyst.

The products of the present invention are useful for the control of various plant and water-infesting pests. Representative of the plant-infesting pests which are controlled by the compounds of the present invention are southern army worms, Mexican bean beetles and aphids. In a representative operation for the control of southern army worms, 7-dimethylamino-4-indanyl methylcarbamate was dispersed in water to prepare an aqueous spray composition containing 100 parts per million by weight or" the dialkylaminoindanyl methylcarbamate per million parts by weight of ultimate spray mixture. This composition was applied to cranberry bean plants in amounts sufiicient to wet the foliage. The leaf surfaces were then allowed to dry and the plants infested with a known number of southern army worm larvae. About 3 days after infestation, the plants were examined to ascertain the control of southern army worms attributable to the dialkylaminoindanyl methylcarbamate compound. It was found that complete kills of southern army worm larvae were obtained.

The compounds of the present invention are also useful for the control of water pests such as entomostracans, as well as undesirable water plants of various species.

In a representative operation for the control of entomostracans, complete control of Daphnia spp. were obtained when this aquatic pest in aqueous media was exposed to 7-dimethylamino-4-indany1 methylcarbamate at a concentration of 1 part by weight per million parts by weight of medium for 24 hours.

The reactant, 7-dialkylamino-4-indanol used in the preparation of the dialkylaminoindanyl methylcarbamates of the present invention may be prepared by reductive alkylation of 7-arnino-4-indanol. In carrying out this preparation, the 7-amino-4-indanol is reacted with at least 2 molar proportions of an aliphatic aldehyde containing from 1 to 4 carbon atoms, inclusive, and hydogen in the presence of palladium on charcoalcatalyst at a temperature of from 10 to 75 C. and a pressure of from 10 to pounds per square inch to produce the desired 7-dialkylamino-4-indanol.

I claim: 1. A compound having the structure oooNHoEn References Cited in the file of this patent UNITED STATES PATENTS Hartle Ian. 20, 1959 OTHER REFERENCES Kolbezen et al.: Journal of Agricultural and Food Chemistry, vol. 2, pages 864- (1954). 

1. A COMPOUND HAVING THE STRUCTURE 